WO2020100683A1 - Batterie solide - Google Patents

Batterie solide Download PDF

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Publication number
WO2020100683A1
WO2020100683A1 PCT/JP2019/043473 JP2019043473W WO2020100683A1 WO 2020100683 A1 WO2020100683 A1 WO 2020100683A1 JP 2019043473 W JP2019043473 W JP 2019043473W WO 2020100683 A1 WO2020100683 A1 WO 2020100683A1
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WIPO (PCT)
Prior art keywords
electrode layer
solid
electrode
face
state battery
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PCT/JP2019/043473
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English (en)
Japanese (ja)
Inventor
充 吉岡
賢二 大嶋
近川　修
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株式会社村田製作所
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Application filed by 株式会社村田製作所 filed Critical 株式会社村田製作所
Priority to JP2020556115A priority Critical patent/JP7047934B2/ja
Priority to CN201980075029.7A priority patent/CN113016092A/zh
Priority to EP19885317.8A priority patent/EP3883014A4/fr
Publication of WO2020100683A1 publication Critical patent/WO2020100683A1/fr
Priority to US17/243,766 priority patent/US20210249697A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/536—Electrode connections inside a battery casing characterised by the method of fixing the leads to the electrodes, e.g. by welding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid state battery.
  • an electrolyte (electrolyte solution) such as an organic solvent has been conventionally used as a medium for moving ions.
  • electrolyte solution organic solvent
  • the organic solvent used in the electrolytic solution is a flammable substance. Therefore, it is required to enhance the safety of the battery.
  • the solid-state battery is, for example, a solid-state battery having a laminated structure in which one or more positive electrode layers and one or more negative electrode layers are alternately laminated with a solid electrolyte layer in Patent Document 1, and the laminated structure is Disclosed is a solid-state battery having an end face electrode on the end face.
  • the inventors of the present invention omit the collector layer and the collector (for example, a foil), and the electrode layer functions as an electrode and the collector layer or collector. It has been found that the battery characteristics are deteriorated when it has a function as an electric body.
  • one or more positive electrode layers 101 and one or more negative electrode layers 102 are solid electrolyte layers.
  • the positive electrode layer 101 and the negative electrode layer 102 are, as shown in A ′ portion and B ′ portion of FIG. 10, respectively, at the end portions on the end surface electrodes 104a and 104b side with respect to the horizontal plane in cross section.
  • the end face electrodes 104 (104a, 104b) are provided with the take-out portions 140 (140a, 140b) to try to suppress the connection failure between the electrode layers 101, 102 and the end face electrodes 104. ..
  • the positive electrode layer 101 and the negative electrode layer 102 are, as shown in A ′ portion and B ′ portion of FIG. 11, respectively, at the end portions on the side of the end surface electrodes 104a and 104b, the end surfaces being planes perpendicular to the horizontal plane in cross section. Since the electrodes 104a and 104b are electrically connected to the lead-out portions 140a and 140b of the electrodes 104a and 104b, the connection failure between the electrode layers 101 and 102 and the end face electrode 104 is likely to occur.
  • An object of the present invention is to provide a solid-state battery that can more sufficiently suppress the connection failure between the electrode layer (that is, the positive electrode layer and / or the negative electrode layer) and the end face electrode.
  • the present invention is A solid state battery having a laminated structure in which one or more positive electrode layers and one or more negative electrode layers are alternately laminated via solid electrolyte layers,
  • the solid-state battery has positive and negative end-face electrodes on the end faces of the laminated structure, At least one electrode layer of the positive electrode layer and the negative electrode layer has a protrusion protruding toward the end surface electrode of the same polarity as the electrode layer in a cross-sectional view at the end portion of the end surface electrode side of the same polarity as the electrode layer.
  • the present invention relates to a solid-state battery which has a shape and is electrically connected to the end face electrode having the same polarity as the electrode layer.
  • the solid-state battery of the present invention has a structure without a current collecting member, it is possible to more sufficiently suppress the connection failure between the electrode layer (that is, the positive electrode layer and / or the negative electrode layer) and the end face electrode.
  • FIG. 1 is a schematic cross-sectional view of a solid state battery according to a first embodiment of the present invention. It is a schematic cross section of the solid battery concerning the 2nd embodiment of the present invention. It is a schematic cross section of the solid-state battery concerning the 3rd embodiment of the present invention. It is a schematic cross section of the solid battery concerning the 4th embodiment of the present invention. It is a schematic cross section of the solid battery concerning the 5th embodiment of the present invention. It is a schematic cross section of the solid battery concerning the 6th embodiment of the present invention.
  • an enlarged schematic cross-sectional view in the vicinity of a negative electrode layer (or a positive electrode layer) for explaining an example of an end projecting structure that the negative electrode layer (or the positive electrode layer) may have at the end on the end face electrode side.
  • An enlarged schematic cross-sectional view in the vicinity of a negative electrode layer (or a positive electrode layer) for explaining an example of an end projecting structure that the negative electrode layer (or the positive electrode layer) may have at the end on the end face electrode side in the solid battery of the present invention Is.
  • the typical sectional view of an example of the conventional solid state battery is shown.
  • the typical sectional view of an example of the conventional solid state battery is shown.
  • Solid battery The present invention provides a solid state battery.
  • solid state battery refers to a battery whose constituent elements (particularly, the electrolyte layer) are composed of solids, and in a narrow sense, the constituent elements (particularly all constituent elements) are composed of solids. Refers to the "all-solid-state battery” that is constructed.
  • the “solid state battery” in the present specification includes a so-called “secondary battery” that can be repeatedly charged and discharged, and a “primary battery” that can only be discharged.
  • the “solid state battery” is preferably a "secondary battery”.
  • the “secondary battery” is not excessively limited to its name, and may include, for example, an electrochemical device such as “electric storage device”.
  • the “plan view” referred to in the present specification refers to a state (top view) when an object is viewed from above or below along a stacking direction D (or a thickness direction of the solid battery) of layers described below that configure the solid battery. Or bottom view).
  • the “cross-sectional view” in the present specification means a cross-sectional state (cross-sectional view) when viewed from a direction substantially perpendicular to the stacking direction D (or the thickness direction of the solid-state battery) of each layer constituting the solid-state battery. That is.
  • the cross-sectional view when describing the end portions of the positive electrode layer and the negative electrode layer on the end face electrode side is a face parallel to the stacking direction D and passing through two end face electrodes (particularly the distance between the two end face electrodes).
  • a plane parallel to the straight line that defines is a cross-sectional state (cross-sectional view) when the solid-state battery is cut.
  • the “vertical direction” and “horizontal direction” used directly or indirectly in this specification correspond to the vertical direction and the horizontal direction in the drawings, respectively. Unless otherwise specified, the same reference numeral or sign indicates the same member / site or the same meaning. In a preferable aspect, it can be considered that the downward direction in the vertical direction (that is, the direction in which gravity acts) corresponds to the “downward direction” and the opposite direction corresponds to the “upward direction”.
  • the solid-state battery 100 of the present invention is, for example, in each of FIGS. 1 to 6, denoted by reference numerals “100A”, “100B”, “100C”, “100D”, “100E” and “100F” (hereinafter simply referred to as “100”).
  • a layered structure (particularly a layered structure or a layered structure) is provided. That is, in the solid-state battery 100 of the present invention, one or more positive electrode layers 1 and one or more negative electrode layers 2 are alternately laminated with the solid electrolyte layer 3 interposed therebetween, and the end face electrode 4 (4a) is formed on the end face of the laminated structure. 4b).
  • the end face of the laminated structure is a face (so-called side face) parallel to the laminating direction, including the end faces of the laminated layers.
  • the end surface electrodes 4a and 4b are usually formed on two end surfaces facing each other in the laminated structure.
  • the number of layers of the positive electrode layer 1 and the negative electrode layer 2 is arbitrary and is not particularly limited.
  • the solid-state battery of the present invention may have a parallel structure or a series structure. 1 to 6 are schematic cross-sectional views of solid-state batteries according to first to sixth embodiments of the present invention, respectively.
  • the electrode layer includes a positive electrode layer 1 and a negative electrode layer 2.
  • the electrode layer is a layer having both a battery reaction function and a current collecting function, that is, contains an active material and an electron conductive material.
  • the positive electrode layer 1 contains a so-called positive electrode active material and an electronically conductive material, and may further contain a solid electrolyte material and / or a bonding material described later.
  • the positive electrode layer 1 is usually composed of a sintered body containing positive electrode active material particles and electron conductive material, and the positive electrode active material particles, electron conductive material particles, and optionally solid electrolyte particles and / or bonding. It may be made of a sintered body containing a conductive material.
  • the negative electrode layer 2 includes a so-called negative electrode active material and an electronically conductive material, and may further include a solid electrolyte material and / or a bonding material described later.
  • the negative electrode layer 2 is usually composed of a sintered body containing negative electrode active material particles and electron conductive material, and the negative electrode active material particles, electron conductive material particles, and optionally solid electrolyte particles and / or bonding. It may be made of a sintered body containing a conductive material.
  • the positive electrode active material contained in the positive electrode layer and the negative electrode active material contained in the negative electrode layer are substances involved in the transfer of electrons in the solid battery, and the ions contained in the solid electrolyte material forming the solid electrolyte layer are the positive electrode and the negative electrode. Charging / discharging is performed by moving (conducting) between and transferring electrons.
  • the positive electrode layer and the negative electrode layer are particularly preferably layers capable of inserting and extracting lithium ions or sodium ions. That is, the solid battery of the present invention is preferably a solid secondary battery in which lithium ions or sodium ions move between the positive electrode and the negative electrode through the solid electrolyte layer to charge and discharge the battery.
  • the positive electrode active material contained in the positive electrode layer is not particularly limited, and examples thereof include a lithium-containing phosphate compound having a Nasicon type structure, a lithium-containing phosphate compound having an olivine type structure, a lithium-containing layered oxide, and a spinel type structure. At least one selected from the group consisting of lithium-containing oxides and the like.
  • lithium-containing phosphate compounds having a Nasicon type structure include Li 3 V 2 (PO 4 ) 3 and the like.
  • Examples of lithium-containing phosphate compounds having an olivine structure include LiFePO 4 , LiMnPO 4, and the like.
  • the lithium-containing layered oxide include LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2, and the like.
  • Examples of lithium-containing oxides having a spinel structure include LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4 .
  • a sodium-containing phosphate compound having a Nasicon type structure a sodium-containing phosphate compound having an olivine structure, a sodium-containing layered oxide and a sodium-containing spinel structure are contained. At least one selected from the group consisting of oxides and the like can be mentioned.
  • the negative electrode active material contained in the negative electrode layer is not particularly limited, and examples thereof include oxides and graphite containing at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb, and Mo. At least one selected from the group consisting of a lithium compound, a lithium alloy, a lithium-containing phosphate compound having a NASICON type structure, a lithium-containing phosphate compound having an olivine type structure, and a lithium-containing oxide having a spinel type structure. Be done.
  • lithium alloys include Li-Al and the like.
  • Examples of the lithium-containing phosphate compound having a NASICON type structure include Li 3 V 2 (PO 4 ) 3 and Li 3 Fe 2 (PO 4 ) 3 .
  • Examples of lithium-containing oxides having a spinel structure include Li 4 Ti 5 O 12 and the like.
  • the negative electrode active material capable of occluding and releasing sodium ions includes a group consisting of a sodium-containing phosphate compound having a Nasicon type structure, a sodium-containing phosphate compound having an olivine type structure, and a sodium-containing oxide having a spinel type structure. At least one selected from
  • the electron conductive material contained in the positive electrode layer and the negative electrode layer is not particularly limited, and examples thereof include metal materials such as silver, palladium, gold, platinum, aluminum, copper, nickel; and carbon materials.
  • metal materials such as silver, palladium, gold, platinum, aluminum, copper, nickel; and carbon materials.
  • carbon is preferable because it hardly reacts with the positive electrode active material, the negative electrode active material, and the solid electrolyte material, and is effective in reducing the internal resistance of the solid battery.
  • the solid electrolyte material that may be included in the positive electrode layer and the negative electrode layer may be selected from the same materials as the solid electrolyte material that may be included in the solid electrolyte layer described below, for example.
  • the bonding material that may be included in the positive electrode layer and the negative electrode layer may be selected from, for example, the same materials as the bonding materials that may be included in the bonding site described below.
  • the positive electrode layer and the negative electrode layer may each independently further include a sintering aid.
  • the sintering aid is not particularly limited and includes, for example, at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, boron oxide, silicon oxide, bismuth oxide, and phosphorus oxide. Can be
  • the thickness of the electrode layer is not particularly limited and is, for example, independently 2 ⁇ m or more and 50 ⁇ m or less, and from the viewpoint of further and sufficiently suppressing the connection failure between the electrode layer and the end face electrode. , Preferably 5 ⁇ m or more and 30 ⁇ m or less, more preferably 5 ⁇ m or more and 20 ⁇ m or less.
  • the total number of laminated layers of the positive electrode layer 1 and the negative electrode layer 2 is not particularly limited, and may be, for example, 2 or more and 2000 or less, and particularly 2 or more and 200 or less.
  • a part of the electrode layers may have the current collecting layer 5.
  • the positive electrode layer 1 has the current collecting layer 5, but all the electrode layers are from the viewpoint of further improving the energy density of the solid-state battery. It is preferable not to have the current collecting layer 5.
  • the current collecting layer may have the form of a foil, but it is preferable to have the form of a sintered body from the viewpoint of reducing the manufacturing cost of the solid battery by integral firing and the internal resistance of the solid battery.
  • the current collecting layer When the current collecting layer has the form of a sintered body, it may be composed of, for example, a sintered body containing electron conductive material particles and a sintering aid.
  • the electron conductive material included in the current collecting layer may be selected, for example, from the same material as the electron conductive material included in the electrode layer.
  • the sintering aid contained in the current collecting layer may be selected from the same materials as the sintering aid contained in the electrode layer, for example.
  • the thickness of the current collecting layer is not particularly limited, and may be, for example, 1 ⁇ m or more and 5 ⁇ m or less, and particularly 1 ⁇ m or more and 3 ⁇ m or less.
  • the solid electrolyte layer 3 is composed of a sintered body containing solid electrolyte particles.
  • the material of the solid electrolyte particles (that is, the solid electrolyte material) is not particularly limited as long as it can provide ions (for example, lithium ions or sodium ions) that can move (conduct) between the positive electrode layer and the negative electrode layer.
  • the solid electrolyte material include a lithium-containing phosphate compound having a Nasicon structure, an oxide having a perovskite structure, an oxide having a garnet type or a garnet type similar structure, and the like.
  • An example of the lithium-containing phosphate compound having a Nasicon structure is Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 and the like.
  • oxides having a perovskite structure include La 0.55 Li 0.35 TiO 3 and the like.
  • oxides having a garnet-type or garnet-type similar structure include Li 7 La 3 Zr 2 O 12 and the like.
  • Examples of the solid electrolyte capable of conducting sodium ions include sodium-containing phosphate compounds having a Nasicon structure, oxides having a perovskite structure, and oxides having a garnet-type or garnet-type similar structure.
  • the sodium-containing phosphate compound having a NASICON structure, Na x M y (PO 4 ) 3 (1 ⁇ x ⁇ 2,1 ⁇ y ⁇ 2, M is, Ti, Ge, Al, from the group consisting of Ga and Zr At least one selected).
  • the solid electrolyte layer may include a sintering aid.
  • the sintering aid included in the solid electrolyte layer may be selected from the same materials as the sintering aid that may be included in the electrode layer, for example.
  • the thickness of the solid electrolyte layer is not particularly limited, and may be, for example, 1 ⁇ m or more and 15 ⁇ m or less, particularly 1 ⁇ m or more and 5 ⁇ m or less.
  • the end face electrodes 4 are electrodes formed on the end faces of the laminated structure, and are usually positive and negative end face electrodes (4a and 4b, respectively) formed on two end faces facing each other in the laminated structure. Each of the end face electrodes 4a and 4b may be formed on the entire surface or a part of the end face of the laminated structure.
  • the end surface electrodes 4a and 4b are preferably formed on the entire surface of the end surface of the laminated structure from the viewpoint of further sufficiently suppressing the connection failure between the electrode layer and the end surface electrode.
  • the end face of the laminated structure is a face (so-called side face) parallel to the laminating direction, including the end faces of the laminated layers.
  • the end face electrode 4 is usually composed of a sintered body containing particles of an electron conductive material and a sintering aid.
  • the electron conductive material included in the end face electrode 4 may be selected, for example, from the same material as the electron conductive material that can be included in the electrode layer.
  • the sintering aid included in the end face electrode 4 may be selected from the same materials as the sintering aid that may be included in the electrode layer, for example.
  • the thickness of the end face electrode is not particularly limited, and may be, for example, 1 ⁇ m or more and 20 ⁇ m or less, and particularly 1 ⁇ m or more and 10 ⁇ m or less.
  • the solid-state battery 100 of the present invention may include the joint portion 6, as described below.
  • the joining portion is a portion responsible for joining the electrode layer and the end face electrode having the same polarity as the electrode layer.
  • the joining portion 6 is usually made of a sintered body containing a joining material.
  • the adhesive material for example, particles
  • the adhesive material is an inorganic material that is easily bonded at the interface between these particles when contacting and sintering the constituent material (for example, particles) of the electrode layer and the constituent material (for example, particles) of the end face electrode. It is a system particle.
  • the bonding material may or may not have electronic conductivity and / or ionic conductivity. Examples of the bonding material include silica glass (SiO 2 ), SiO 2 , and PbO, B 2 O 3 , MgO, ZnO, Bi 2 O 3 , Na 2 O, Al 2 O 3 , CaO, and BaO. Examples thereof include composite oxide glass and the like.
  • the bonding portion 6 may further include an electron conductive material, a solid electrolyte material, and / or a sintering aid in addition to the bonding material.
  • the electron conductive material included in the bonding portion 6 may be selected, for example, from the same material as the electron conductive material that may be included in the electrode layer.
  • the solid electrolyte material included in the bonding portion 6 may be selected from the same materials as the solid electrolyte material that may be included in the solid electrolyte layer, for example.
  • the sintering aid included in the bonding portion 6 may be selected from the same materials as the sintering aid that may be included in the electrode layer, for example.
  • the thickness of the joint portion 6 is not particularly limited, and may be the same as the thickness of the electrode layer to be joined to the end face electrode.
  • the solid state battery of the present invention has a structure without a current collecting member.
  • the current collecting member-less structure is a structure in which at least one of the positive electrode layer and the negative electrode layer does not have a current collecting member such as a current collecting layer and a current collector (for example, foil).
  • a current collecting member such as a current collecting layer and a current collector (for example, foil) is a member that exclusively exhibits a current collecting function without directly contributing to a battery reaction (for example, electron generation reaction). Therefore, the electrode layer having a function as an electrode and a function as a current collector is different.
  • the electrode layer having a structure without a current collecting member has both a function as an electrode and a function as a current collector.
  • the fact that the electrode layer has both a function as an electrode and a function as a current collector means that the electrode layer not only performs a battery reaction (charge / discharge reaction), but also moves electrons generated by the reaction to the end face electrode or It means that it can be induced.
  • Electrode layers such as a positive electrode layer and a negative electrode layer that also have these functions usually include an active material and an electronically conductive material, and do not require a current collector such as a foil or another member such as a current collecting layer, Can be moved to the end face electrode.
  • both electrode layers of the positive electrode layer 1 and the negative electrode layer 2 may have a structure without a current collecting member.
  • one of the electrode layers may have a structure without a current collecting member.
  • the negative electrode layer 2 has a current collecting member-less structure
  • the positive electrode layer 1 has a current collecting member (for example, a current collecting layer) 5.
  • the negative electrode layer 2 may have a current collecting member (for example, a current collecting layer)
  • the positive electrode layer 1 may have a current collecting member-less structure.
  • both the positive electrode layer 1 and the negative electrode layer 2 have a collector-less structure.
  • both electrode layers of the positive electrode layer 1 and the negative electrode layer 2 are provided in order to further sufficiently suppress the connection failure between the electrode layer and the end face electrode and further improve the energy density of the solid battery. It is preferable to have a structure without a current collecting member and also to have an end protruding structure described later.
  • At least one of the positive electrode layer 1 and the negative electrode layer 2 (particularly the electrode layer having a structure without a current collecting member) has an end projecting structure as shown in FIGS. 1 to 6.
  • the end projecting structure means that the electrode layer (particularly the electrode layer having a structure without a current collecting member) is on the side of the end surface electrode 4 (4a, 4b) having the same polarity as the electrode layer.
  • the end surface electrodes 4a and 4b having the same polarity as the electrode layer have a projecting shape projecting toward the end surface electrode side having the same polarity as the electrode layer in a cross-sectional view. It is a structure that is electrically connected to.
  • the positive electrode layer 1 (particularly, the positive electrode layer 1 having a current collecting member-less structure) has a cross-sectional view at the end portion (A1 to A6) on the end face electrode 4a side of the positive electrode. While having a protruding shape protruding toward the end face electrode of the positive electrode, it is electrically connected to the end face electrode 4a of the positive electrode.
  • the negative electrode layer 2 (particularly, the negative electrode layer 2 having a structure without a current collecting member) has a cross-sectional view at the end portions (B1 to B6) of the end face electrode 4b side of the negative electrode, as shown in FIGS.
  • the end face electrode 4b of the negative electrode is electrically connected to the end face electrode 4b of the negative electrode while having a protruding shape protruding toward the end face electrode of the negative electrode.
  • the electrode layers 1 and 2 have a protruding shape at the end portions (A1 to A6 and B1 to B6) on the side of the end surface electrode 4 (4a, 4b) having the same polarity as the electrode layer. In a cross-sectional view, it projects toward the end surface electrode 4 (4a, 4b) having the same polarity as the electrode layer.
  • the positive electrode layer 1 has a protruding shape at the end portion (A1 to A6) on the positive electrode end surface electrode 4a side, and the protruding shape projects toward the positive electrode end surface electrode 4a side in a cross-sectional view.
  • the negative electrode layer 2 has a projecting shape at the end portions (B1 to B6) on the side of the end surface electrode 4b of the negative electrode, and the projecting shape projects toward the end surface electrode 4b of the negative electrode in cross-sectional view. ..
  • the end portions (A1 to A6 and B1 to B6) of the electrode layers 1 and 2 on the side of the end surface electrode 4 (4a, 4b) have a projecting shape that protrudes toward the end surface electrode of the same polarity as the electrode layer in a sectional view. This means that the end face of the end portion of the electrode layer is not shown by a vertical line in a sectional view.
  • the end portions (A1 to A6 and B1 to B6) on the side of the end surface electrode 4 (4a, 4b) having the same polarity as the electrode layer are as shown in FIGS.
  • An end face electrode having the same polarity as that of the electrode layer with reference to vertical lines X and Y passing through a point J farthest from the end face electrode 4 among points on a line segment that defines the end face of the end portion in a cross-sectional view. 4 (4a, 4b) side Za, Zb is projected.
  • the end portions (A1 to A6) of the positive electrode on the side of the end surface electrode 4a have a point on a line segment that defines the end surface of the end portion in sectional views, as shown in FIGS.
  • a vertical line X passing through the point J which is the most distal from the end face electrode 4a, it projects toward the positive end face electrode 4a (Za direction).
  • the end portions (B1 to B6) of the negative electrode on the end surface electrode 4b side are points on a line segment that defines the end surface of the end portion in cross-sectional view, as shown in FIGS.
  • a vertical line Y passing through the point J farthest from the end face electrode 4b is used as a reference, and the end face electrode 4b of the negative electrode projects toward the end face electrode 4b (Zb direction).
  • the vertical line means a straight line perpendicular to the horizontal plane.
  • the end portions (A1 to A6 and B1 to B6) of the electrode layers 1 and 2 on the end face electrode 4 (4a, 4b) side are directly connected to the end face electrodes 4 (4a, 4b) having the same polarity as the electrode layer. It may be connected or indirectly connected.
  • the end portion is directly connected to the end surface electrode means that the end portions A1 and B1 in FIG. 1, the end portions A2 and B2 in FIG. 2, the end portion A3 in FIG. 3, the end portion B4 in FIG. 5 means that the end portion is directly and electrically connected to the end face electrode 4 like the end portion B5.
  • the end portion being indirectly connected to the end surface electrode means that the end portion is connected to the end surface electrode 4 via the joint portion 6 described later, as in the end portion A5 of FIG.
  • the end portion of the electrode layer is indirectly and electrically connected to the end face electrode 4 via the joint portion 6, the joint strength of the electrode layer with respect to the end face electrode can be increased, and the battery characteristics due to the joint failure can be improved. The decrease can be suppressed more sufficiently. Further, when the color of the bonding portion 6a of the positive electrode layer 1 and the color of the bonding portion 6b of the negative electrode layer 2 are different, it becomes easy to distinguish the positive electrode layer and the negative electrode layer.
  • the solid-state battery of the present invention has the end projecting structure at the end portion of the electrode layer such as the positive electrode layer 1 and / or the negative electrode layer 2 on the end surface electrode side, the electrode layer is connected to the end surface electrode or the bonding portion.
  • the electrode layer is connected to the end surface electrode or the bonding portion.
  • the projecting length L of the projecting shape in the end projecting structure of the electrode layer is usually 5 ⁇ m or more and 500 ⁇ m or less, and preferably 10 ⁇ m or more from the viewpoint of further adequately suppressing the poor connection between the electrode layer and the end face electrode. It is 100 ⁇ m or less.
  • the protrusion length L of the protrusion shape is the horizontal direction from the point J, which is the most distal to the end surface electrode, to the point K, which is the most proximal to the end surface electrode, among the points on the line segment that defines the end surface of the end portion. It refers to length (ie distance) (see, eg, FIGS. 1-6, 7A, 8A and 9A).
  • An end projecting structure that the electrode layer may have (for example, a connecting surface structure between the end surface electrode-side end portions of the electrode layers 1 and 2 and the end surface electrode 4 and end surface electrode-side end portions of the electrode layers 1 and 2).
  • the structure of the connecting surface with the joint portion 6) is not particularly limited as long as the end has a projecting shape.
  • an end projecting structure that the electrode layers 1 and 2 may have (for example, a connecting surface structure between the end portions of the electrode layers 1 and 2 on the end surface electrode side and the end surface electrode 4 and the end surface electrodes of the electrode layers 1 and 2). 1 to 6 (particularly, the ends A1 to A6 and B1 to B6 in these figures) and FIGS. 7A to 7T, the step surface is formed stepwise.
  • the stepped structure may include one or more protruding portions having a protruding shape.
  • an inclined structure including one or more protruding portions having a linear protruding shape may be used.
  • 9A to 9P it may have a curved structure including at least one portion having a projecting shape protruding in a curvilinear manner, or may have a composite structure thereof.
  • 7A to 7T, 8A to 8P, and 9A to 9P are all end protruding structures in which the negative electrode layer (or the positive electrode layer) may have an end portion on the end face electrode side in the solid state battery of the present invention.
  • FIG 3 is an enlarged schematic cross-sectional view in the vicinity of a negative electrode layer (or a positive electrode layer) for explaining an example.
  • 7A to 7T, 8A to 8P, and 9A to 9P show a structural example in which the negative electrode layer 2 is joined to the end face electrode 4b on the left side (particularly, its complementary shape portion 40b) on the left side.
  • a structural example when the positive electrode layer 1 is joined on the left side to the positive electrode side end face electrode 4a (particularly its complementary shape portion 40a) is also shown.
  • the protrusion length (length in the end surface electrode direction Z (Za, Zb)) L1 of each step portion, L2 and L3 may be such that the cumulative protruding length or the maximum protruding length of all the step portions is within the range of the protruding length L.
  • the heights H, H1, H2, H3, and H4 of the respective step portions are electrode layers which will be described later.
  • the thickness may be equal to or less than the thickness.
  • the heights H, H1, H2, H3, and H4 of the respective step portions are usually independently 1 ⁇ m or more and 30 ⁇ m or less, and from the viewpoint of further sufficiently suppressing the connection failure between the electrode layer and the end face electrode, It is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 1 ⁇ m or more and 10 ⁇ m or less, and further preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • the protrusion lengths (lengths in the end surface electrode direction Z (Za, Zb)) L1, L2, and L3 of all the inclined portions are all
  • the cumulative protrusion length or the maximum protrusion length in the inclined portion may be within the range of the protrusion length L.
  • the heights H, H1, H2, H3, and H4 of the respective inclined portions are such that the total height of all the inclined portions is equal to or less than the thickness of the electrode layer described later. Good.
  • the heights H, H1, H2, H3, and H4 of the inclined portions are usually independently 1 ⁇ m or more and 30 ⁇ m or less, and from the viewpoint of further sufficiently suppressing the connection failure between the electrode layer and the end face electrode, It is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 1 ⁇ m or more and 10 ⁇ m or less, and further preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • the protrusion lengths (lengths in the end surface electrode direction Z (Za, Zb)) L1, L2, and L3 of all the curved portions are all
  • the cumulative protrusion length or the maximum protrusion length at the curved portion of the above may be within the range of the above protrusion length L.
  • the heights H, H1, H2, H3, and H4 of the respective curved portions are such that the total height of all the curved portions is equal to or less than the thickness of the electrode layer described later. Good.
  • the heights H, H1, H2, H3, and H4 of the respective curved portions are usually independently 1 ⁇ m or more and 30 ⁇ m or less, and from the viewpoint of further sufficiently suppressing the connection failure between the electrode layer and the end face electrode, It is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 1 ⁇ m or more and 10 ⁇ m or less, and further preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • both electrode layers of the positive electrode layer 1 and the negative electrode layer 2 (in particular, both electrode layers having a structure without a current collecting member). May have an end protruding structure, or, as shown in FIGS. 3 to 4, one electrode layer (particularly one electrode layer having a structure without a current collecting member) has an end protruding structure. May have.
  • the positive electrode layer 1 has an end projecting structure
  • the negative electrode layer 2 may have an end protruding structure.
  • both electrode layers of the positive electrode layer 1 and the negative electrode layer 2 are provided from the viewpoints of further sufficiently suppressing the connection failure between the electrode layer and the end face electrode and further improving the energy density of the solid battery. It is preferable to have an end protruding structure, and more preferably to have an end protruding structure and a structure without a current collecting member.
  • the positive electrode layer 1 has an end protruding structure
  • not all of the positive electrode layers 1 have to have the end protruding structure.
  • the outermost positive electrode layer 1 does not have to have an end protruding structure.
  • the outermost positive electrode layer 1 is the uppermost positive electrode layer and / or the lowermost positive electrode layer.
  • all the positive electrode layers 1 have an end projecting structure from the viewpoint of further sufficiently suppressing the connection failure between the electrode layer and the end face electrode and further improving the energy density of the solid-state battery. It is preferable to have an end projecting structure and a structure without a current collecting member.
  • the negative electrode layer 2 has a projecting end portion structure
  • all the negative electrode layers 2 have a projecting end structure in order to further sufficiently suppress the connection failure between the electrode layer and the end face electrode and further improve the energy density of the solid-state battery. It is preferable to have an end projecting structure and a structure without a current collecting member.
  • the end face electrodes 4 (4a, 4b) are, for example, in a sectional view, As shown in FIG. 1 and FIG. 2, there is a complementary shape part 40 (40a, 40b) that has a shape complementary to the end of the electrode layer on the end face electrode side.
  • the complementary shape portion 40 (40a, 40b) constitutes a part of the end face electrode 4 (4a, 4b) and has a complementary shape corresponding to the end protruding structure (particularly protruding shape) of the electrode layer. And is usually made of the same material as the end face electrode 4.
  • the complementary shaped portion 40 (40a, 40b) of the end face electrode 4 (4a, 4b) projects to the side of the electrode layers 1 and 2 having the same polarity as the end face electrode 4. That is, the complementary shaped portion 40a of the positive electrode side end surface electrode 4a projects toward the positive electrode layer 1, and the complementary shaped portion 40b of the negative electrode side end surface electrode 4b projects toward the negative electrode layer 2.
  • the complementary shape has, for example, the contact or fitting with the end portions of the electrode layers 1 and 2 on the side of the end faces (particularly the protruding shape thereof) with a clearance as close as possible to 0 mm (particularly 0 mm). It is a possible shape.
  • the electrode layers 1 and 2 (particularly the end portion on the end surface electrode side) and the end surface electrode 4 (4a, 4b) (particularly the complementary shape portion 40 (40a, 40a, 40b) 40b)) connection and consolidation have been achieved.
  • the electrode layers 1 and 2 (particularly the end portion on the end surface electrode side) are the end surface electrodes 4 (4a, 4b) (particularly their complementary shapes).
  • the part 40 (40a, 40b)) and the sintered body are integrally sintered.
  • the integral sintering of the sintered bodies means that two or more members adjacent to or in contact with each other are joined by sintering.
  • the electrode layers 1 and 2 are sintered bodies, It is preferable that they are integrally sintered from the viewpoint of further sufficiently suppressing the defective connection between the electrode layer and the end face electrode.
  • the end portions of the electrode layers 1 and 2 on the end surface electrode side are directly and electrically connected to the end surface electrodes 4 (4a, 4b), the end portions of the electrode layers 1 and 2 on the end surface electrode side are 2, FIG. 7A, FIG. 7F, FIG. 7G, FIG. 7L, FIG. 7Q to FIG. 7T, FIG. 8A, FIG. 8B, FIG. 8D, FIG. 8F, FIG. 8G, FIG. 8I to FIG. 8L, FIG. 8N to FIG.
  • the end face electrodes 4 (4a, 4b) are directly and electrically connected over the entire end face. Connected to each other.
  • the end portions of the electrode layers 1 and 2 on the end surface electrode side may be indirectly and electrically connected to the end surface electrodes 4 (4a, 4b) via the joint portions 6 (6a, 6b).
  • the bonding strength of the electrode layer with the end surface electrode is further increased, and the battery performance is improved due to the poor bonding between the electrode layer and the end surface electrode. The decrease can be suppressed more sufficiently.
  • the joint portion 6 (6a, 6b) (particularly, the end portion on the electrode layer side) has a complementary shape that is complementary to the end portions of the electrode layers 1 and 2 in a cross-sectional view, as shown in FIG. 6, for example. It is preferable to have the parts 60 (60a, 60b).
  • the complementary shape portion 60 (60a, 60b) is a member having a complementary shape corresponding to the end projecting structure (particularly projecting shape) of the electrode layer while forming a part of the joining portion 6 (6a, 6b).
  • the complementary shape portion 60 (60a, 60b) of the bonding portion 6 (6a, 6b) projects to the electrode layer 1, 2 side. That is, the bonding portion 6a of the positive electrode layer 1 projects toward the positive electrode layer 1, and the bonding portion 6b of the negative electrode layer 2 projects toward the negative electrode layer 2.
  • the complementary shape of the complementary shape portion 60 (60a, 60b) is, for example, as close as possible to 0 mm (particularly 0 mm) with respect to the end portion of the electrode layers 1 and 2 on the end surface electrode side (particularly its protruding shape). It is a shape that can abut or fit with clearance.
  • the electrode layers 1 and 2 (particularly the end portion on the end face electrode side) and the bonding portion 6 (6a, 6b) (particularly the complementary shape portion 60 (60a, 60a, 60b) 60b)) connection and mating have been achieved.
  • the electrode layers 1 and 2 (especially the end portion on the end face electrode side) are formed by integrally sintering the joint portions 6 (6a, 6b) (particularly the complementary shape portions 60 (60a, 60b)) and the sintered bodies. Is preferred.
  • the integral sintering of the sintered bodies means that two or more members adjacent to or in contact with each other are joined by sintering.
  • the bonding portion 6 is usually composed of a material different from the constituent materials of the electrode layer (the positive electrode layer 1 and / or the negative electrode layer 2) and the end face electrode 4.
  • the bonding portion 6 is composed of a material having a different kind and / or a mixing ratio of constituent materials from the constituent material of the positive electrode layer 1, the constituent material of the negative electrode layer 2 and the constituent material of the end face electrode 4 (and the solid electrolyte layer 3). Has been done.
  • the joint portion 6 (6a, 6b) is opposite to the complementary shape portion 60 (60a, 60b) at the joint portion in the end portion on the end face electrode side (that is, in the horizontal direction in cross section).
  • End portion has an end protruding structure.
  • the end projecting structure of the joining portion is similar to the end projecting structure of the electrode layer, and as shown in FIG. 6, the joining part 6 has end portions (C6 and C6) on the end surface electrodes 4 (4a, 4b) side.
  • D6) is a structure that is electrically connected to the end face electrodes 4a and 4b while having a projecting shape protruding toward the end face electrode side in a sectional view. Specifically, as shown in FIG.
  • the joint portions 6 (6a, 6b) of the electrode layers project at the end portions (C6 and D6) on the side of the end surface electrodes 4 (4a, 4b) having the same polarity as the electrode layers. It has a shape, and the projecting shape projects to the end surface electrode side having the same polarity as the electrode layer in a cross-sectional view.
  • the bonding portion 6a of the positive electrode layer 1 has a protruding shape at the end portion (C6) on the end surface electrode 4a side of the positive electrode. It projects to the end surface electrode 4a side.
  • the bonding portion 6b of the negative electrode layer 2 has a projecting shape at the end portion (D6) on the side of the end surface electrode 4b of the negative electrode, and the projecting shape is a negative electrode in cross section. Of the end face electrode 4b.
  • the end surface of the end portion on the electrode side having the same polarity as the electrode layer is not shown by a vertical line in a sectional view.
  • the end C6 on the end face electrode 4a side of the positive electrode is, as shown in FIG. 6, a point on a line segment that defines the end face of the end in cross-sectional view.
  • a vertical line X ′ passing through a point J ′ that is most distal from the end face electrode 4 a is used as a reference, and the end face electrode 4 a protrudes toward the end face electrode 4 a side (Za direction).
  • the end portion D6 on the side of the end surface electrode 4b of the negative electrode is, as shown in FIG. 6, the end surface among the points on the line segment that defines the end surface of the end portion in cross-sectional view.
  • a vertical line Y ′ that passes through the point J ′ that is most distal from the electrode 4b it projects toward the end face electrode 4b side (Zb direction) of the negative electrode.
  • the end portions (C6 and D6) on the end face electrode 4 (4a, 4b) side of each of the joining portions 6 (6a, 6b) are directly connected to the end face electrode 4 (4a, 4b).
  • the end portion being directly connected to the end surface electrode means that the end portion is directly and electrically connected to the end surface electrode 4 like the end portions C6 and D6 in FIG. ..
  • the joint portion 6 (6a, 6b) has an end projecting structure at the end portion on the end face electrode side, the joint portion 6 (6a, 6b) can be joined "intricately" to the end face electrode. As a result, it is possible to further increase the bonding area between the end face electrode and the bonding portion, as compared with the case where the end projecting structure is not provided. For this reason, the electrode layer is firmly connected to the end face electrode via the bonding portion, and it is possible to more sufficiently suppress deterioration of battery characteristics due to defective bonding.
  • the protruding length L'of the protruding shape in the end protruding structure of the joining portion 6 (6a, 6b) is independent of the protruding length L of the protruding shape in the end protruding structure of the electrode layer described above. It may be a value within the same range as the length L.
  • the protrusion length L ′ is usually 5 ⁇ m or more and 500 ⁇ m or less, and preferably 10 ⁇ m or more and 100 ⁇ m or less from the viewpoint of further sufficiently suppressing the connection failure between the electrode layer and the end face electrode.
  • the protrusion length L ′ of the protrusion shape is the horizontal distance from the point J ′ that is the most distal to the end face electrode to the point K ′ that is the most proximal from the end face electrode among the points on the line segment that defines the end face of the end portion. It is the length (i.e., distance) in a direction (see, for example, Fig. 6).
  • the end projecting structure that can be included in the joining portion 6 (6a, 6b) (for example, the connecting surface structure between the end portion of the joining portion 6 (6a, 6b) on the end face electrode side and the end face electrode 4) is the end portion. Is not particularly limited as long as it has a protruding shape.
  • the end projecting structure that the joint portion 6 (6a, 6b) may have (for example, the connecting surface structure between the end portion of the joint portion 6 (6a, 6b) on the end face electrode side and the end face electrode 4) is as described above.
  • the structure may be an inclined structure including one or more linearly protruding projecting portions, or may be a curved structure including one or more curvilinearly projecting projecting portions. However, it may be a composite structure of these.
  • the projecting length and height of each step in the step structure, the projecting length and height of each inclined part in the tilted structure, and each curve in the curved structure may be the same as in the end projecting structure of the electrode layers 1 and 2, respectively.
  • the end portions of the electrode layers 1 and 2 on the end face electrode side are indirectly and electrically connected to the end face electrodes 4 (4a, 4b) via the joint portions 6 (6a, 6b), and the joint portions 6 are end faces.
  • the end surface electrode 4 (4a, 4b) has a cross-sectional view, for example, as shown in FIG. It has a complementary shape portion 40 (40a, 40b) that is a complementary shape to the end portion on the end face electrode side.
  • the complementary shape portion 40 (40a, 40b) has a complementary shape corresponding to the end projecting structure (particularly projecting shape) of the joining portion 6 while forming a part of the end surface electrode 4 (4a, 4b).
  • the complementary shape portion 40 (40a, 40b) of the end face electrode 4 (4a, 4b) projects to the side of the electrode layers 1 and 2 having the same polarity as that of the end face electrode 4 (that is, the joint portion 6 side). That is, the complementary shaped portion 40a of the positive electrode side end surface electrode 4a projects toward the positive electrode layer 1, and the complementary shaped portion 40b of the negative electrode side end surface electrode 4b projects toward the negative electrode layer 2.
  • the complementary shape of the complementary shape portion can be fitted to the end portion on the end face electrode side of the joining portion 6 (particularly its protruding shape) with a clearance as close as possible to 0 mm (particularly 0 mm).
  • the integral sintering of the sintered bodies means that two or more members adjacent to or in contact with each other are joined by sintering.
  • the electrode layers 1 and 2 (especially the end portion on the end face electrode side) and the bonding portion 6 (6a, 6b) (particularly their complementary shape portions 60 (60a, 60b)) are sintered bodies, It is preferable that they are integrally sintered from the viewpoint of further sufficiently suppressing the defective connection between the electrode layer and the end face electrode. From the viewpoint of further sufficiently suppressing the connection failure between the electrode layer and the end face electrode, the electrode layers 1 and 2 (in particular, the end portion on the end face electrode side) are connected to the joint portion 6 (6a, 6b) (particularly the complementary portion thereof).
  • the shape portion 60 (60a, 60b)) and the end surface electrode 4 (4a, 4b) (particularly the complementary shape portion 40 (40a, 40b)) and the sintered body are integrally sintered.
  • the complementary shape portions 40 (40a, 40b) are all sintered bodies, but it is more sufficient that the electrode layers and the end face electrodes are connected to each other by being integrally sintered. It is more preferable from the viewpoint of suppression.
  • the electrode layer 1 As shown in FIG. 6, the end portions of the electrodes 2 and 2 on the side of the end surface are directly and electrically connected to the joint portion 6 (6a, 6b) (particularly, the complementary shape portion 60 (60a, 60b)) as shown in FIG. May be connected physically.
  • the bonding portion contains an electronically conductive material as well as the bonding material.
  • the bonding portion may further include a constituent material of the electrode layer and / or a constituent material of the end face electrode.
  • the end portions of the electrode layers 1 and 2 on the end face electrode side are directly and electrically connected to the joint portion 6 over the entire end faces thereof, so that the joint strength of the end face electrodes of the electrode layers (particularly the joint of the electrode layers is The bonding strength with the end face electrode via the portion) is further increased, and the deterioration of the battery performance due to the poor bonding between the electrode layer and the end face electrode can be further sufficiently suppressed.
  • the electrode layer 1 7B, 7E, 7H to 7K, 7M to 7P, 8C, 8E, 8H, 8M, 9G, 9H and 9J As shown, a part of the end face is directly and electrically connected to the joint portion 6 (6a, 6b) (particularly the complementary shape part 60 (60a, 60b)), and the rest of the end face is It may be directly and electrically connected to the end surface electrode 4 (4a, 4b) (in particular, the complementary shape portion 40 (40a, 40b) thereof).
  • the bonding site includes the bonding material, and may or may not further include the electron conductive material.
  • the bonding portion may further include a constituent material of the electrode layer and / or a constituent material of the end face electrode.
  • the end portions of the electrode layers 1 and 2 on the end face electrode side are directly and electrically connected to the joint portion 6 at a part of the end face, and the rest of the end face is directly and electrically connected to the end face electrode 4. Connection to the end face electrode of the electrode layer (particularly the end face electrode via the end portion of the electrode layer via the end face electrode) and the effect of improving the balance between the effect of improving the smooth movement of electrons. Excel.
  • the bonding strength of the electrode layer with the end surface electrode is further increased, but also electrons can be moved more smoothly.
  • FIG. 7B to 7E, 7H to 7K, 7M to 7P, 8C, 8H, 8M, 9G, and 9J only one junction portion 6b ( Alternatively, 6a) may be used, or two or more bonding sites 6b1 and 6b2 may be used in each electrode layer, as shown in FIGS. 8E and 9H.
  • the joint strength of the electrode layer with the end face electrode is further increased. be able to.
  • the two or more bonding sites are provided between the end surface electrode-side end of the electrode layer and the end surface electrode as shown in FIGS. 8E and 9H. , May be arranged in parallel in the moving direction of electrons (for example, the horizontal direction in the drawing), or may be arranged in series.
  • the two or more bonding sites are mainly the bonding site excellent in electronic conductivity (for example, one of 6b1 or 6b2) and the bonding property mainly between the electrode layer and the end face electrode.
  • the bonding site mainly having excellent electron conductivity contains the bonding material and the electron conductive material, and further contains the constituent material of the electrode layer and / or the constituent material of the end face electrode. But it is okay.
  • the bonding site (for example, the other of 6b1 or 6b2) having excellent bonding property between the electrode layer and the end face electrode mainly contains the bonding material and does not contain the electron conductive material.
  • the bonding portion mainly having excellent bonding property between the electrode layer and the end surface electrode may further include a constituent material of the electrode layer and / or a constituent material of the end surface electrode.
  • the facing area of the two electrode layers is large in the stacking direction.
  • the end portion where each electrode layer has a protruding shape on the end face electrode side is arranged as follows.
  • the end portion of each electrode layer having a projecting shape on the end face electrode side is arranged outside the region between the electrode layers immediately above and immediately below that having a polarity different from that of the electrode layer, as shown in FIG. 1, for example. ..
  • each negative electrode layer having a protruding shape on the end face electrode side is arranged outside the region between the positive electrode layers immediately above and immediately below it. Further, for example, it is preferable that the end portion of each positive electrode layer having a protruding shape on the end face electrode side is arranged outside the region between the negative electrode layers immediately above and immediately below it.
  • the end portions where each electrode layer has a projecting shape on the end face electrode side have, for example, as shown in FIG. It is preferably arranged in a region that does not overlap with the electrode layer.
  • each negative electrode layer having a projecting shape on the end face electrode side are arranged in regions that do not overlap the positive electrode layer immediately above and immediately below, for example, as shown in FIG. Is preferably provided.
  • the end portions of each positive electrode layer having a protruding shape on the end face electrode side are, for example, as shown in FIG. It is preferably arranged.
  • the bonding site 6 of each electrode layer is preferably arranged as follows:
  • the bonding portion of each electrode layer is preferably disposed outside the region between the electrode layers immediately above and immediately below which have polarities different from those of the electrode layer.
  • the bonding portion of each negative electrode layer is arranged outside the region between the positive electrode layers directly above and directly below it.
  • the joining portion of each positive electrode layer is preferably arranged outside the region between the negative electrode layers immediately above and directly below it.
  • the bonding portions of the electrode layers are, as shown in, for example, FIG. 6, in regions that do not overlap with the electrode layers immediately above and below the electrode layers having polarities different from those of the electrode layers. It is preferably arranged.
  • the bonding portion of each negative electrode layer is arranged in a region that does not overlap with the positive electrode layer immediately above and immediately below, as shown in FIG. 6, for example.
  • each positive electrode layer is arranged in a region that does not overlap with the negative electrode layer immediately above and immediately below, as shown in FIG. 6, for example.
  • the electrode layers (the positive electrode layer 1 and the negative electrode layer 2), the solid electrolyte layer 3 and the end face electrodes 4 (and the bonding portion 6) are formed from the viewpoint of reducing the manufacturing cost of the solid-state battery by integral firing. More preferably, they are integrally sintered. That is, it is preferable that the electrode layers (the positive electrode layer 1 and the negative electrode layer 2), the solid electrolyte layer 3 and the end face electrodes 4 (and the bonding portions 6) are all sintered bodies, but are integrally sintered.
  • the color of the end face electrode be different on the positive electrode side (4a) and the negative electrode side (4b).
  • the color of the end face electrode be different on the positive electrode side (4a) and the negative electrode side (4b).
  • bonding materials of different colors may be mixed as the constituent material of each end face electrode, or different colors of the end face electrodes may be mixed. Glass or ceramics may be added to the bonding material for coloring.
  • the solid-state battery of the present invention may have any shape in a plan view, and usually has a rectangular shape. Rectangular shapes include squares and rectangles.
  • the solid state battery 100 of the present invention can be manufactured by a printing method such as a screen printing method, a green sheet method using a green sheet, or a composite method thereof.
  • a printing method such as a screen printing method, a green sheet method using a green sheet, or a composite method thereof.
  • the printing method is adopted will be described in detail, but it is obvious that the method is not limited to the method.
  • the method for manufacturing a solid-state battery of the present invention is A step of forming an unfired laminate by a printing method; and a step of firing the unfired laminate.
  • a laminated body in which layers and members other than the end face electrode are laminated may be formed by a printing method, and the end face electrode may be formed on the end face of the obtained laminated body (that is, a laminated structure) by a coating method such as a dipping method.
  • the end surface electrode may be formed in part or in whole by a vapor phase method such as a sputtering method and / or a vapor deposition method.
  • Each paste is a predetermined constituent material of each layer (member) selected from the group consisting of the above-mentioned positive electrode active material, negative electrode active material, electron conductive material, solid electrolyte material, bonding material, and sintering aid, It can be prepared by wet mixing an organic vehicle with an organic material dissolved in a solvent.
  • the organic material contained in the paste is not particularly limited, but a polymer compound such as polyvinyl acetal resin, cellulose resin, polyacrylic resin, polyurethane resin, polyvinyl acetate resin, or polyvinyl alcohol resin can be used.
  • the solvent is not particularly limited as long as it can dissolve the organic material, and for example, toluene, ethanol, etc. can be used.
  • media can be used, and specifically, ball mill method, viscomill method, etc. can be used.
  • a wet mixing method which does not use a medium may be used, and a sand mill method, a high pressure homogenizer method, a kneader dispersion method or the like can be used.
  • the base material is not particularly limited as long as it can support the unbaked laminate, and for example, a polymer material such as polyethylene terephthalate can be used.
  • a base material having heat resistance to the firing temperature is used.
  • print layers are sequentially laminated with a predetermined thickness and pattern shape, and an unfired laminated body corresponding to a predetermined solid battery structure is formed on a base material.
  • a plurality of print layers are sequentially laminated in a predetermined pattern shape by dividing the print layer from the bottom to the top with a predetermined thickness.
  • a drying process that is, a solvent evaporation process
  • the unsintered laminate may be peeled from the substrate and subjected to the firing step, or may be subjected to the firing step while the unsintered laminate is held on the substrate. Good.
  • Firing process The green stack is fired.
  • the firing is performed by removing the organic material at, for example, 500 ° C. in a nitrogen gas atmosphere containing oxygen gas, and then heating at, for example, 550 ° C. to 1000 ° C. in the nitrogen gas atmosphere.
  • Firing may be normally performed while applying pressure to the unfired laminated body in the laminating direction D (in some cases, the laminating direction D and the direction M perpendicular to the laminating direction D).
  • the pressing force is not particularly limited and may be, for example, 1 kg / cm 2 or more and 1000 kg / cm 2 or less, and particularly 5 kg / cm 2 or more and 500 kg / cm 2 or less.
  • the solid-state battery according to the embodiment of the present invention can be used in various fields where electricity storage is expected.
  • the solid-state battery according to an embodiment of the present invention is merely an example, and is used in the electric / information / communication field in which a mobile device or the like is used (for example, a mobile phone, a smart phone, a smart watch, a laptop computer, a digital camera, an activity).
  • Mobile devices such as volume meters, arm computers, and electronic papers), household and small industrial applications (for example, power tools, golf carts, household / care / industrial robots), large industrial applications (forklifts, etc.) Elevators, bay port cranes), transportation system fields (for example, hybrid vehicles, electric vehicles, buses, trains, electrically assisted bicycles, electric motorcycles, etc.), power system applications (for example, various types of power generation, road conditioners, smart grids) , General home-installed power storage systems, etc.), medical applications (fields of medical devices such as earphone hearing aids), medical applications (fields of dose management systems, etc.), IoT fields, space / deep sea applications (for example, space exploration). Field, such as aircraft and diving research vessels).
  • household and small industrial applications for example, power tools, golf carts, household / care / industrial robots), large industrial applications (forklifts, etc.) Elevators, bay port cranes), transportation system fields (for example, hybrid vehicles, electric vehicles, buses, trains, electrically assisted bicycle

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

La présente invention concerne une batterie solide dans laquelle une défaillance de connexion entre une couche d'électrode (c'est-à-dire, une couche d'électrode positive et/ou une couche d'électrode négative) et une électrode de surface d'extrémité peut être suffisamment supprimée. La présente invention porte sur une batterie solide ayant une structure empilée dans laquelle une ou plusieurs couches d'électrodes positives et une ou plusieurs couches d'électrodes négatives sont empilées alternativement avec une couche d'électrolyte solide intercalée entre elles : ladite batterie solide ayant les électrodes de surface d'extrémité d'électrodes positives et négatives aux surfaces d'extrémité de la structure empilée ; et au moins une couche parmi les couches d'électrodes négatives et les couches d'électrodes négatives ayant une forme de saillie, laquelle se projette vers le côté d'électrode de surface d'extrémité ayant la même polarité que la couche parmi les couches d'électrodes positives et les couches d'électrodes négatives, à l'extrémité du côté d'électrode de surface d'extrémité ayant la même polarité que la couche parmi les couches d'électrodes positives et les couches d'électrodes négatives, dans une vue de section, et étant connectées électriquement à l'électrode de surface d'extrémité ayant la même polarité que la couche parmi les couches d'électrodes positives et les couches d'électrodes négatives.
PCT/JP2019/043473 2018-11-16 2019-11-06 Batterie solide WO2020100683A1 (fr)

Priority Applications (4)

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JP2020556115A JP7047934B2 (ja) 2018-11-16 2019-11-06 固体電池
CN201980075029.7A CN113016092A (zh) 2018-11-16 2019-11-06 固体电池
EP19885317.8A EP3883014A4 (fr) 2018-11-16 2019-11-06 Batterie solide
US17/243,766 US20210249697A1 (en) 2018-11-16 2021-04-29 Solid state battery

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JP2018-215570 2018-11-16
JP2018215570 2018-11-16

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EP (1) EP3883014A4 (fr)
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WO2021039043A1 (fr) * 2019-08-23 2021-03-04 株式会社村田製作所 Batterie à semi-conducteur
WO2022080404A1 (fr) * 2020-10-16 2022-04-21 株式会社村田製作所 Batterie à semi-conducteur

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WO2022080404A1 (fr) * 2020-10-16 2022-04-21 株式会社村田製作所 Batterie à semi-conducteur

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CN113016092A (zh) 2021-06-22
EP3883014A4 (fr) 2024-04-17
JP7047934B2 (ja) 2022-04-05
EP3883014A1 (fr) 2021-09-22
US20210249697A1 (en) 2021-08-12
JPWO2020100683A1 (ja) 2021-09-02

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